Novel detergent compositions



NOVEL nornuonrrr ooltarosrrrons Henry B. Hess, Summit, NJ, and Foster l). Snell, New York, and Lloyd 1. Usipow, Monscy, NFL, and William C. York, deceased, late of Westhury, NFL, by Ruth M. York, administrutrix, Mineula, N.Y., assignors to Sugar Research Foundation, lncu, New York, F132, a corporation of New York No Drawing. Filed Feb. 11, 1955, er. No. 714,495

9 Claims. (Cl. 252-135) This application is a continuation-in-part of our copending applications, Ser. No. 480,288, filed lanuary 6, 1955, now abandoned, and Ser. No. 552,281, filed December 12, 1955, now Patent No. 2,893,990, issued Sul y 7, 1959.

This invention relates to novel detergent compositions comprising as a surface active agent a mono-ester of sucrose or raffinose and a fatty acid containing from about 6 to 30 carbon atoms. These mono-esters are those which are produced in accordance with our said copending application Ser. No. 552,281, now Patent No. 2,893,990, and these mono-esters and the preparation are disclosed in detail in said application. In its preferred form, the invention relates to novel detergent compositions suitablefor washing and laundering of the type referred to by the art as a built detergent.

It is an object of the present invention to provide novel detergent compositions containing a surface-active agent comprising a mono-ester of sucrose or railinose and a fatty acid containing from about 6 to 30 carbon atoms.

It is another object of the present invention to provide novel detergent compositions which are economically produced from materials which are in abundant supply and available at low cost.

It is a further object of the present invention to provide novel solid detergent compositions containing a surface active agent which is of extremely low toxicity and which is non-irritating to the human epidermis.

It is also an object of the present invention to provide novel heavy duty detergent compositions of the class referred to as a built detergent having low foaming properties.

Additional objects will be apparent to those skilled in the art from reading the specification which follows.

The present invention results from our discovery that mono-esters of sucrose and ramnose and a fatty acid containing from about 6 to 30 carbon atoms, as disclosed and claimed in our said copending application Ser. No. 552,281, new Patent No. 2,893,990, possess excellent detergent properties, and provide particularly suitable and advantageous detergent compositions for heav -duty use when incorporated with a builder. These monoesters are compatible with both cationic and anionic surface active agents. They can tolerate the calcium and magnesium ions present in hard waters to a greater ex i tent than can the anionic surface active agents and they tend to be less tenaciously adsorbed on the substrate than either the anionic or cationic surface-active agents of the prior art. The novel detergent compositions of the invention can be produced at an extremely low cost per pound and possess free-flowing properties which permits their convenient packaging, dispensing and use in laundering. Detergent compositions containing the monoesters of sucrose or ralfinose are less irritating to the skin and mucous membranes as a result of the non-irritating properties of said esters. Many are valuable because of their low foaming properties. Fruits and vegetables may be thoroughly cleansed with the detergent compositions of the invention without spoiling their. flavor, and residues which remain. are harmless.

The novel detergent compositions of the. present invention comprise a surface-active agent comprising a mono-ester of sucrose or rafiinose and a fatty: acid containing from about 6 to 30 carbon atoms produced in accordance with our said copending application Ser. No. 552,281, new Patent No. 2,893,990. The surface-active component of these detergent compositions may contain it Heavy duty detergent compositions in accordance. with the invention suitable for laundering and washing desirably contain a builder. poncnt are the alkali-metal salts of a molecularly dehydrated phosphoric acid. Among the suitable molecularly dehydrated phosphates are sodium tripolyphosphate,

tctrasodium pyrophosphate, sodium hexametaphosphatm:

sodium tetraphosphate and the corresponding potassium.

salts. Potassium tripolyphosphate and tetrapotassium. pyrophosphate are commercially available potassium.

salts. Because of their lower costs, the sodium molecularly dehydrated phosphates are most suitable for use in powder detergent compositions. The preferred molecularly dehydrated phosphates are sodium tripolyphosphate.

and tetrasodium pyrophosphate.

Detergent compositions in accordance with the present invention of the built or heavy-duty class desirably also contain an alkaline salt of an alkali-metal.

the suitable alkali-metal alkaline salts are the metal phosphates, silicates, tetraborates, carbonates, bicarbonates and sesquicarbonates. Preferably the alkalimetal alkaline salt employed shall be one of the following: trisodium phosphate, sodium silicate, borax, sodium carbonate, sodium bicarbonate and sodium sesquicarbonate, although the corresponding potassium salts maybe employed. The most desirable alkaline salt is sodium silicate. The chief function of the sodium silicate is that Y of corrosion inhibitor.

Built detergent compositions in accordance with the invention may also contain various amounts of neutral cularly sodium carboxymethylcellulose, imparts soil-susv pending properties to the compositions which makes the compositions particularly suitable when used for, laundering purposes.

Patented Feb. 7, 1 961 Suitable as a builder. com-.

Among alkali- Another, optional component. is .the. brightening agent sometimes referred to as .axicptical bleaching agent. Typical brightening agents are stilbene derivatives, such as Tinopal BVA (Geigy Co., Inc.) and Blancophor A-3 (General Dyestulf Corp).

The surface-active agent shall desirably constitute from about 10 to 40%, and preferably from about 15 to 25%, of the compositions. The molecularly dehydrated phosphates usually. desirably constitute from about 10 to 90%, and preferably from about 15 to 55%, of the composition. An alkali-metal alkaline salt, other than a molecularly dehydrated phosphate, when employed, shall usually desirably constitute from about 2 to 20% and preferably from about 3 to 10%, of the composition. Parts are expressed in terms of precent by weight. Listed below are the desirable range limits of the components of a built heavy-duty detergent composition according to the present invention.

Listed below are the preferred ranges of components expressed in terms of parts by weight.

Component: Parts by Weight Surface-active agent 15 to 25 Molecularlydehydrated phosphate 30 to 60 Sodium silicate. 3 to 1 Sodium earboxymethylcellulose 0. E to 1.5

Additional inert components may also be present. Thus, ordinary sucrose which may be introduced along with the sucrose mono-ester employed as a surface-active agent may be present. The other ingredients may also have present additional inert ingredients which provide no useful function in the detergent composition. The composition may also contain moisture, such as about 5% by weight.

'Heavy duty or built detergent compositions in accordance with the invention should have an alkalinity such that when a 1% aqueous solution is prepared from them itjwill have a pH value of between about 9.0 and 10.0. This is an important characteristic of the compositions of the present invention since those compositions producing solutions having a higher alkalinity may cause the mono-ester of sucrose or raffinose to hydrolyze, whereas compositions producing a solution of lower alkalinity may have impaired detergent action.

The heavy-duty or built detergent compositions in accordance with the invention possess superior detergency since the mono-ester of sucrose or ratfinose has its detergent properties syuergized by the molecularly dehydrated phosphates.

For washing purposes the built or heavy duty detergent compositions in accordance with this invention are desirably employed for laundering purposes in the form of a 0.1% to 0.5% aqueous solution.

The mono-ester of sucrose or ralfinose employed as a surface-active agent in the detergent compositions of the invention are described in detail in our said copending application, Ser. No. 552,281, now Patent No. 2,893,990. These mono-esters contain a fatty-acid moiety containing from about 6 or 8 to 30 carbon atoms, inclusive and desirably from about 12 to 22 carbon atoms. inclusive. Among the fatty acids which. may constitute the fatty- -acid moiety of the mono-esters of sucrose or raffinose are the saturated fatty acids, including: lauric, myristic, palmitic, stea'ric acids, etc., and the unsaturated fatty acids and preferably mono-unsaturated fatty acids, including: A -dodecylenic, palmitoleic, oleic acids, etc., or mixture of about the boiling point of the alcohol and sweep- 4, tures of these acids. The fatty acid moiety includes those higher molecular-weight carboxylic acids derived from naturally-occurring materials, such as the so-called rosin acids obtained from rosin or from tall oil. The principal component of rosin is abietic acid and its anhydride, which constitute about -90% of the resin and nearly 50% of tall oil consists of resin acids of analogous structure.

The fatty acid moiety of the mono-esters of sucrose or raffinose is desirably a mixture of fatty acids obtained from naturally-occurring glyceridic oils and fats. These glyceridic fats and oils include: tallow, coconut oil, sperm-whale oil, lard, lard oil, cocoa butter, palm oil, castor oil, corn oil, olive oil, soya bean oil, bearing oil, menhaden oil, etc. The resulting mixed mono-esters coritain the fatty acids initially present in the fats and oils in relatively the same proportions in which they occurred in the original fats and oils and the final product appears to have superior properties over those esters containing but a single fatty acid. I

The mono-esters of sucrose or raffinose contemplated for use in the invention are those produced in accordance with our said copending application Set. No. 552,231, new Patent No. 2,893,990, by reacting a non-sucrose or non-raffinose ester of a fatty acid with sucrose or raffinose. The reaction is desirably conducted in an arm matic, aliphatic, alicyclic or heterocyclic solvent having an amide group or constituent or a solvent which is a heterocyclic or aliphatic tertiary amine, or a dialkylsul foxide. The reaction mixture shall contain an alkaline catalyst. Preferably, substantially anhydrous conditions are employed as even small amounts of moisture may retard the rate of reaction. The reaction is produced by heating the reaction mixture at a temperature of from about 20 C. up to about 180 C. The optimum tem perature range is from about 60 to C. At the lower temperatures the reaction products are less colored.

The reaction time required is usually between about 30 minutes to 24 hours, depending somewhat upon the temperature of the reaction mixture and the alkalinity of the catalyst, although 2 to 5 hours is generally preferred. The non-sucrose and non-ralfinose esters of the fatty acids employed as starting materials and as a source of fatty acids may be simple esters of mono-hydric alcohol, such a methyl palmitate, methyl stearate, ethyl laur'ate, methyl abietate, ethyl abietate, etc., or they may be esters of a polyhydroxy alcohol, or polyol, where the hydroxyl groups of the alcohol are on adjacent carbon atoms, such as the diand tri-esters of glycerol.

"In producing the mono-esters of sucrose or raifinose for use as a surface-active agent in our detergent compositions, we prefer to employ as the non-sucrose or nonralfinose starting ester, an ester of a fatty acid and a readily volatile alcohol, such as the lower monohydric alcohols, methanol or ethanol. The volatile alcohol is preferably stripped from the reaction mixture by distillation, desirably under reduced pressure, as it is liberated during the formation of the sucrose or raffinose ester. This permits a more rapid reaction and provides higher yields of the sucrose or raffinose esters, and accomplishes a separation of the volatile alcohol from the reaction solvent and the reaction products. Where it is desired to employ mixed fatty acids, such as mixtures which occur in mixed, naturally-occurring glyceridic esters, we prefer to first convert the glyceridic esters to mixed esters of a volatile alcohol by reacting the glyceridic esters with an alcohol to produce an ester interchange. As an alternative to vacuum distillation, the volatile alcohol may be removed from the reaction mixture by heating the mixture at substantially atmospheric pressure to a temper...-

ing the system with an inert gas, such as air or nitrogen,

which will not react with the reactants or the reaction products to any substantial degree. I

Among the suitable solvents which may be employed for the reaction in producing the mono-esters of sucrose or rafiinose are such tertiary amines as: trimethylamine, triethylamine, N-methylmorpholine, pyridine, quinoline, pyrazine, methylpyrazine, N,N-dimethylpiperazine, etc., such amides as: formamide, N,N,-dimethylformamide, N-methyl-Z-pyrrolidone, etc. Dimethylsulfoxide is an excellent solvent. Other solvents may be suitably employed. The solvent material employed may contain other additional polar groups in the moleculealthough such groups preferably exclude mercapto, hydroxyl, ester, primary and secondary amino groups. Desirably the amine or amide shall have not more than 6 carbon atoms for each nitrogen atom present in the molecule and the total number of carbon atoms shall not exceed 12. The preferred solvents employed to date are N,N-dimethy1- formamide and dimethylsulfoxide. We prefer to employ a solvent which is less volatile than the alcohol of the non-sucrose or non-ratfinose ester starting material.

Among the alkaline catalysts which may be employed in producing the mono-esters of sucrose and rafiinose are several types of metals, hydroxides, inorganic salts and organic compounds, including alkali-metal hydroxides, such as potassium, sodium and lithium hydroxides, salts of an alkali-metal and a weak acid, such as sodium carbonate, potassium carbonate, etc.; or such alkaline salts as trisodium phosphate; oralkali-metal alcoholates, such as sodium methoxide, potassium ethoxide, sodium ethoxide; or organic bases, such as the quaternary ammonium bases, including the mixed alkyl-dimethylbenzyl ammonium hydroxides, the alkyl-trimethyl ammonium hydroxides and tetra-allcyl quaternary ammonium hydroxides, such as tetra-methyl ammonium hydroxide, cetyl-dimethyl-benzyl ammonium hydroxide, etc.; or the alkali-metal sucrates or rafiinates, such as sodium sucrate, sodium raffinate, etc. Additionally metals, such as tin and zinc may be employed. Alkaline salts and alkalimetal carbonates, and particularly potassium carbonate, are the preferred catalysts.

Generally speaking, the alkaline catalysts which are satisfactory are those which are soluble in the solvents employed and which, when added in a 1% w./v. concentration in a 0.5% W./V. phenolphthalein solution in a solvent containing equal parts by volume of boiled N,N- dimethylformamide and carbon dioxide-free Water, gives the characteristic alkaline phenolphthalein magenta color. The phenolphthalein solution is prepared by first boiling the N,N-dimethylformamide for minutes to remove volatile amines. One gram of phenolphthalein is dissolved in 100 ml. of the boiled N,N-dimethylformamide and 100 ml. of carbon dioxide-free water is added. When 0.1 gram of the alkaline catalyst is added to 10 m1. of the resulting phenolphthalein indicator solution, it should give the well known pinkish-purple or magenta color of alkaline phenolphthalein solutions.

The purification and recovery of mono-esters of sucrose or rafiinose is disclosed in detail in our said copending application Ser. No. 552,281, now Patent No. 2,893,990.

In order more clearly to disclose the nature of the present invention, specific examples illustrating the present invention will hereinafter be described. It should be understood, however, that this is done solely by way of example and is intended neither to delineate the scope of the invention nor limit the ambit of the appended claims. Where conversion yields are reported in some of the examples which follow, it is intended to refer to the ratio of sucrose converted to ester compared with the sucrose not recovered from the reaction mixture in a form suitable for recycling. Parts are expressed in terms of parts by weight, unless otherwise stated.

Examples 1 through 7, inclusive, hereinbelow are examples of heavy duty detergent compositions in accordance with the invention containing sucrose mono-esters as the principal source or" surface active agent. In place of the sucrose mono-esters listed, the corresponding rafdnose mono-ester may be employed.

Parts by Weight Example Number. 1 2 3 4 5 6 7 8 Sucrose monotallowate (Example 110) Sucrose monoco- Sucrose monooleate (Example Sodium tripolyphosphate Tetrasodiurn pyrophosphate. Sodium silica-re (N 2.20 :Si 02 1:3. Sodium silicate (N 8.2OISiOg =11) Sucrosc 22. 0 Sodium chloride... Sodium sulfate Sodium carboxymethylccllulosa Moisture Sodium dodecylbenzene sulio' nate ests show that a detergent composition containing mixtures of two or more sucrose mono-esters, such as mixtures of sucrose mono-tallowate and mono-cocoate provide better detergency than the same amount of only 1 one such ester.

For the sake of brevity, Examples 9 through 113, inclusive, are presented hereinbelow in condensed form. Examples 9 through 43 consist of combining each of the surface active agent combinations a through g, inclusive, of part A, with each of the builder combinations 1 through 5, inclusive, of part B, in the proportions of 15 parts by weight of surface-active agent combination with 85 parts by weight of builder combination. Examples 44 through 78, inclusive, consist of combining each of the surface active agent combinations 0 through g, inclusive, of part A, with each of the builder combinations 1 through 5, inclusive, of part B in the proportions of 20 parts by weight of surface-active agent combination with parts by weight or" builder combination. Examples 79 through 113, inclusive, consist of combining each of the surface-active agent combinations [1 through g, inclusive, of part A, with each of the builder combinations 1 through 5, inclusive; of part B in the proportions of 25 parts by weight of surface-active agent com bination with 75 parts by weight of builder combination. The surface-active components and builder components employed to provide these consolidated examples are listed below:

Examples 9 through 113 PART ASURFACE-ACTIVE AGENTS a b c d e f g Sucrose mono-neonate (Ex. 117) 75 40 40 50 40 20 Sucrose mon0-tallowatc (Ex. 116) t0 20 Lauryl isopropanolarnide 25 20 20 20 20 ,Dodccylhenzene sullonate.sodiun1 salt. 40 40 Tallowsultate, sodium salt 50 Laurylsull'ate, sodium salt 50 40 PART B Sodium tripolyphosphate 50.0 40.0 35.0 50.0 30.0 Tct-rasodium pyrophosphate. 12.5 15.0 15.0 16.0 30.0 Sodium s11 ate (NazOzSiOi- 0.0 7. 5 5.0 7.0 6.0 Sucrose 29.0 10.0 10.0 5.0 Sodium sulfate..." 21.4 43.0 16.0 28.0 Sodium bicarbonate 0 Sodium carboxymothylcellulose. 1. 5 1.0 1.0 0.9 0.0 Optical bleach 0.05 0.05 0.05 0.05 0.05

crose or raflinose with the fatty acid alkanolamides or sodium dodecylbenzene sulfonate give better detergency than the individual surface-active agent. Thus mixtures of sucrose mono-cocoate or mono-tallowate with lauryl isopropanolamide or sodium dodecylbenzene sulfonate are superior to each of the individual agents used alone in the same amount with the same builder composition.

As will be apparent to those skilled in the art from the teachings of this invention, various other sucrose or raffinose mono-ester mixtures may be employed in the foregoing examples as well as other molecularly dehydrated phosphates. Furthermore, the proportions of each of the components of the compositions may be varied considerably within the proportion ranges contemplated by'the invention. 7

In Examples 114 through 124 below are illustrative examples disclosing the preparation of mono-esters of sucrose or raffinose suitable for employment as the surface active component of the detergent compositions of the present invention.

Example 114 and the bomb was heated for about 15 hours at about 160C. About /2 of the solvent (dimethylformarnide) was removed by vacuum distillation. The remaining solution was cooled to nearly room temperature, after which unreacted distearin was precipitated. The precipitate was removed by filtration and the filtrate was extracted three times with equal volumes of hexane. The resulting dimethylformamide solution was further distilled in vacuo to a thick syrup, which was precipitated with acetone, and filtered. The acetone solution was evaporated, producing a residue which was composed of 22 grams (0.036 mole) of relatively pure sucrose monostearate, having a melting point of about 52-53 C.; [a] =+33.2, for an absolute yield of 24.6% based upon the amount of distearin employed in the reaction. The unreactcd sucrose filtered above was dried to be used in subsequent processes. Pure sucrose mono-stearate was found to have a melting point of 52-53 C. and

V 2 Example 115 A solution was prepared by suspending about 100 grams (0.293 mole) of sucrose in 600 ml. of pyridine. With this suspension was mixed about 173 grams (0.195

mole) of tristearin dissolved in 300 ml. of pyridine.

About 5 grams of sodium methoxide were added to the mixture after which the mixture was heated in a closed pressure bomb for 15 hours ata temperature of approximately 150" C. A major fraction of the pyridine was vdistilled under vacuum from the reaction mixture and Example 116 v A solution was prepared by dissolving about 100 grams (0.293 mole) of sucrose in 500ml. of N,N-dimethy1- formamide. To the resulting solution was added about 170 grams (0.195 mole) of inedible-grade tallow, a cornmercial fat ordinarily derived from beef tallow. (The tallow contained a fatty-acid composition of approximately 25% palrnitic, 24% stearie, 42% oleic, 2% my ristic, 2% palrnitoleic, with the remainder of the fatty acids composition being unaccounted for.) To the result-- ing mixture was added about 3 grams of sodium methoxide and the mixture was then placed in a pressure bomb and heated in the closed bomb to a temperature of about to C. for 15 hours. About /2 of the dimethylformarnide was distilled under vacuum and unreacted fat was allowed to separate and was then removed. The remaining dimethylformarnide solution was purified as described in Example 114. The amount of sucrose monotallowate which was recovered indicated a conversion yield of about 25%.

Example 117 The procedure of Example 116 was repeated except that the tallow fat dissolved in pyridine was replaced with a solution of about 116 grams (0.175 mole) of coconut oil dissolved in 400 ml. of N,N-dimethylformamide. (The coconut oil contained a fatty acid content of about 45% lauric, 18% myristic, 10% palmitic and 8% oleic acids. The remainder of the fatty acids content was made up of small percentages other saturated and unsaturated acids.) About 35 grams (0.066 mole) of sucrose monococoate were obtained for a yield of about 37.5% based upon the amount of coconut oil employed.

Example 118 A solution was prepared by dissolving about 100 grams (0.293 mole) of sucrose in 500 ml. of N,N-dimethylformamide. With this solution was mixed about 62 grams (0.20 mole) of methyl laurate dissolved in 400 ml. of of dimethylforrnamide. About 2 grams of sodium methoxide were added to the resulting mixture and the mixture placed in a pressure bomb where it was heated in the closed bomb for 8 hours at a temperature of about 130 C. The reaction mixture was distilled to remove /2 its volume and the residue cooled. Upon cooling, unreacted methyl laurate separated and was recovered. The remaining dimethylforrnamide solution was extracted twice with equal volumes of hexane after which an amount of acetone equal to 5 times the volume of the dimethylformamide solution was added to said dimethylforrnamidesolution. The material which then precipitated from the resulting acetone-dimethylformamide solution was removed" by filtration and the filtrate was distilled to give a residue which, when recrystallized from acetone, produced 20 grams of sucrose mono-laurate (MP. 72-80 C.; [a] =+52.0) to provide a conversion yield of about 50%. Pure sucrose mono-laurate was found to have a melting point'of 909l C. and [a] =+42.5.

Example 119 Example 120 A ZOO-gram (0.397 mole) portion of previously desiccated raffinose was dissolved in 800 ml. of dry N,N-dimethylformamide. To this was added grams (0.263 mole) of coconut oil. The resulting solution was heated to 90 C. and kept at this temperature for 12 hours with constant stirring. During this time four l-gram portions.

of sodium methoxide catalyst were added. At the completion of the reaction, the solution was extracted four times with equal volumes of hexane. The resulting dimethylformamide solution was distilled under a vacuum of 1.0 mm. mercury until a thick syrup was obtained.

This syrup 'was diluted with seven volumes of acetone and Example 121 Employing completely dry materials, about 387 grams of sucrose were dissolved in 1275 ml. of dimethylformamide by heating with vigorous agitation. 112.5 grams of methyl stearate and 7.5 grams of potassium carbonate were added to the solution. The resulting reaction mixture was maintained at 9095' C. at a pressure of 80 to 100 mm. of mercury. The methanol produced during the course of the reaction was stripped from the system as it formed by means of a six-plate fractionating column. After 9 to 12 hours, part of the dimethylformamide was distilled and the residue was dried under vacuum. The dry residue was found to contain 53.9% sucrose, 37.9% sucrose monostearate, 1.6% sucrose distearate, methyl stearate, 2.9% potassium stearate and 1.3% potassium carbonate.

Example 122 This example describes the preparation of sucrose monostearate at a temperature of 120 C. The reaction mixture consisted of 387 grams of sucrose, 112.5 grams of methyl stearate, 1275 milliliters of dimethylformamide and 7.5 grams of potassium carbonate. The reaction was carried out at 120 C., 190 to 195 mm. mercury pressure and carbon dioxide-free dry air was bubbled through the reaction mixture. After one hour, 75' percent of the methyl stearate and 75 percent of the theoretical sucrose for monoester formation had reacted. After 2 hours, 80 percent of the methyl stearate and 78 percent of the theoretical sugar had reacted to form sucrose monostearate.

Example 123 This example describes the preparation of sucrose monotallowate. The reaction mixture consisted of about 112.5 grams of methyl tallowate, 387 grams of sucrose, 1275 milliliters of dimethylformamide and 7.5 grams of potassium carbonate. The reaction mixture was substantially anhydrous. The methyl tallowate was produced by subjecting the tallow employed in Example 116, above, to esterexchange with methyl alcohol, in accordance with well-known procedures and removing the glycerol which formed. After heating the reaction mixture for 12 hours at 90 to 95 C., 100 mm. mercury pressure, without sweeping the system with air, the distribution of tallowate was as follows: 5.3% as unreacted methyl tallowate, 2.4% as soap, 66.4% as sucrose monotallowate and 25.9% as sucrose di-tallowate.

At the completion of the reaction, the solution was distilled to remove about 90 percent of the dimethylformamide. Then 500 milliliters of n-butanol and 500 milli liters of water were added to the resulting paste. The

the butanol layer.

Example 124 a A. Employing completely dry materials, 129 grams of sucrose were dissolved in 425 ml. ofdimethylformamide by heating with vigorous agitation. To this solutionwas added 37.5 grams of methyl stearate and 2.5 grams of potassium carbonate. The reaction mixture was maintained at to C. under 80 to mm. mercury pres sure. Dry, carbon dioxide-free air was bubbled through the solution at approximately 100 ml. per minute. A sixplate fractionating column was employed for stripping the methanol from the system. After 10 hours reaction time, the mixture was distilled to dryness. Analysis of this residue showed 76 gram of sucrose monosearate and 86 grams of sucrose.

B. A 100-gram portion of the residue from A above was added to 300 ml. of a 10 percent aqueous sodium chloride solution and 300 ml. of n-butanol. The mixture was warmed, while stirring, until the solids had dis solved completely. The two layers were separated and the butanol layer was washed with two ml. portions of a 10 percent aqueous sodium chloride solution. The butanol layer was distilled to dryness to give a solid residue containing 93 percent sucrose monostearate.

In producing the sucrose or rafiinose mono-esters in these foregoing examples, equimolecular quantities of one or more of the following glyceridic fats or oils may be substituted: sperm-whale oil, lard, lard oil, peanut oil, cocoa butter, palm oil, castor oil, corn oil, olive oil, soya bean oil, herring oil, menhaden oil, etc. The resulting mixed fatty-acid esters of sucrose or raflinose contain a fatty-acid content in relatively the same proportions in which they originally occurred in the initial oil. Other alkaline catalysts may be employed in place of those employed in the examples described hereinabove. In particular, potassium methoxide, sodium ethoxide and other alkali-metal alchohoiates may be satisfactorily employed, as well as alkali-metal sucrates, such as potassium sucrate and alkali-metal hydroxides such as sodium hydroxide and lithium hydroxide. Other solvents may, of course, be employed.

The terms and expressions which we have employed are used as terms of description and not of limitation, and we have no intention, in the use of such terms and expressions, of excluding any equivalents of the features shown and described or portions thereof, but recognize that various modifications are possible within the scope of the invention claimed.

What is claimed is:

1. A heavy-duty detergent composition consisting essentially of from about 10 to 40% by weight of a surface active component comprising a fatty-acid ester selected from the class consisting of a mono-ester of sucrose and rafiinose and a fatty-acid containing between 6 and 30 carbon atoms and as a detergent aid from about 10 to 90% by weight of an alkali-metal salt of a molecularly-dehydrated phosphoric acid.

2. A detergent composition as defined by claim 1 wherein the surface-active component is. a mono-fatty acid ester of sucrose.

3. A heavy duty detergent composition as defined by claim 1 wherein the alkali-metal salt of a molecularlydehydrated phosphoric acid is sodium tripolyp-hosphate.

4. A heavy duty detergent composition as defined by claim 1 wherein the alkali-metal salt of a molecularlydehydrated phosphoric acid is tetrasodium pyrop-hos phate.

5. A heavy duty detergent composition as defined by claim 1 wherein there is also present from about 2 to 20% by weight of sodium silicate.

6. A detergent composition as defined by claim 1 wherein the surface-active component comprises a mix ture of said mono-esters.

7. A detergent composition as defined by claim 1 wherein the surface-active component comprises at least one other surface-active agent selected from the group consisting; of anionic and non-ionic surface active agents,

75 in addition to said mono-fattyacid ester.

8; A detergent composition as defined by claim 6 References Cited in the file of this patent wherein the surface-active component comprises sucrose UNITED STATES PATENTS mono-tallowate and sucrose mono-cocoate.

9. A heavy duty detergent composition consisting esi l /11 7 sentially of from about 15 to 25 parts by weight of a 5 a fi --J l 3'26 1949 surface active component comprising a fatty-acid mono- 2,477,383 eW1S 11 Y 7 ester selected from the class consisting of a mono-ester 2 3 2 508111111 g 3gof sucrose and raffinose with a fatty-acid containing befig 3 3; J 18 5s tween 6 and 30 carbon atoms from about 30 to 60 parts ayton i 19 2,855,367 Buck Oct. 7, 1958 by weightof an alkali-metal salt of a molecularly-de- 10 hydrated phosphoric acid, 3 to 10 parts by weight of an OTHER REFERENCES alkali-metal silicate, and from about 0.3 to 1.5 parts by Chemical Week, Research, New Boost for Sugar," ,weight of an alkali-metal carboxymethylcellulose. September 11, 1954, p. 49.

UNITED STATES PATENT OFFICE CERTIFICATION OF CORRECTION Patent No. 2,970,962 February 7, 1961 Henry B. Hass et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, line 26, for "the" read their column 3, second table, under the heading "Parts byweight", and opposite "Sodium silicate", for "3 t0 1" read 3 to 10 same column, and opposite "Sodium carboxymethylcellulose", for the indistinct entry read 0,3 to 1.5 column 4, line 6, for "resin" read rosin line 14, for "hearing" read herring column 8, line 27, after "percentages" insert of Signed and sealed this 11th day of July 1961o (SEAL) Attest:

ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents 

1. A HEAVY-DUTY DETERGENT COMPOSSITION CONSISTING ESSENTIALLY OF FROM ABOUT 10 TO 40% BY WEIGHT OF A SURFACE ACTIVE COMPONENT COMPRISING A FATTY-ACID ESTER SELECTED FROM THE CLASS CONSISTING OF A MONO-ESTER OF SUCROSE AND RAFFINOSE AND A FATTY-ACID CONTAINING BETWEEN 6 AND 30 CARBON ATOMS AND AS DETERGEN AID FROM ABOUT 10 TO 90% BY WEIGHT OF AN ALKALI-METAL SALT OF A MOLECULARLY-DEHYDRATED PHOSPHORIC ACID. 